CN103502349B - Include the preparation method of the polyethylene blend of the resin of resin and the ziegler-nata production of metallocene-produced - Google Patents

Include the preparation method of the polyethylene blend of the resin of resin and the ziegler-nata production of metallocene-produced Download PDF

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CN103502349B
CN103502349B CN201280021671.5A CN201280021671A CN103502349B CN 103502349 B CN103502349 B CN 103502349B CN 201280021671 A CN201280021671 A CN 201280021671A CN 103502349 B CN103502349 B CN 103502349B
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polyvinyl resin
polyethylene
halogenation
resin
catalyst
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CN103502349A (en
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D.德瓦科特
E.达米
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Total Petrochemicals Research Feluy SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to the preparation methods of homogeneous polyethylene product, and described method includes following steps：(a) the first polyvinyl resin is produced in the reactor in the presence of a metallocene catalyst, first polyvinyl resin has 0.940-0.970g/cm3Density and wherein described first polyvinyl resin have and possess 2-250g/10 minutes MI2Low molecular weight (LMW), the density measures with ASTM D-1505 standardized tests at a temperature of 23 DEG C, the melt index (MI) MI2It is measured using 190 DEG C of temperature and the load of 2.16kg by the program of ASTM D-1238；(b) the second polyvinyl resin is individually produced in the reactor in the presence of Ziegler-Natta catalyst, wherein second polyvinyl resin has the MI for possessing 0.01-15g/10 minutes2High molecular weight (HMW)；(c) make together with first polyvinyl resin and the second polyvinyl resin physical blending to produce the polyethylene product.

Description

Include the polyethylene of the resin of resin and the ziegler-nata production of metallocene-produced The preparation method of blend
Technical field
The present invention relates to the polyethylene product blendings for the resin that the resin comprising metallocene-produced and ziegler-nata produce The preparation method of object.Chemical manufacture is present invention can be advantageously used with, the polymerization of alkene especially ethylene (PE) is especially used for.
Background technology
Polyolefin such as polyethylene (PE) passes through polymerized monomer such as ethylene (CH2=CH2) and synthesize.Because polyolefin is cheap, peace Entirely, it is stable to most of environment and is easily worked, therefore it is useful in numerous applications.Polyethylene can be divided into several Type, such as, but not limited to LDPE (low density polyethylene (LDPE)), LLDPE (linear low density polyethylene) and HDPE (high-density polyethylenes Alkene) and high molecular weight (HMW), middle-molecular-weihydroxyethyl (MMW) and low molecular weight (LMW).All types of polyethylene has different property Matter and characteristic.
Alkene (such as ethylene) polymerization often uses monomer (such as ethylene), diluent and catalysis in circulation flow reactor Agent, optionally activator, optionally one or more comonomers and optionally hydrogen progress.
Polymerization in circulation flow reactor usually carries out under slurry conditions, wherein the polymer produced is typically to suspend The form of solid particle in diluent.Slurry is set continuously to be recycled in the reactor to keep polymer solid particles with pump Effective Suspension in liquid diluent.Polymer slurries are discharged by settling leg from circulation flow reactor, and the settling leg is to divide The principle criticized is run to collect slurry.Solid of the sedimentation for improving the slurry finally collected as product slurry in the leg Concentration.Product slurry is further discharged to by the flash line of heating in flash tank, wherein most diluent and unreacted Monomer be flashed out and recycle.
From reactor collected polymer product and after removing dealkylation residue, dry polymer product obtains polymer tree Fat.Additive can be added, and by mixed with polymers and can finally pelletize, obtain polymer product.
During mixing step, close mixed polymerization resin and optional additive are as uniform as possible to obtain Polymer product.Preferably, mixing is completed in an extruder, wherein each ingredient to be mixed to and made polymer product and is appointed Selection of land some additives fusing so that can occur to mix closely.Then, which at stick, cooling and is granulated, such as with Form pellet (pellet).In this form, the mixture obtained can be subsequently used for manufacturing different objects.Two can be produced respectively Kind or more different polyvinyl resin, and then mix, represent physical blending process.
But complex situations can occur during different vistanexes are prepared into polyolefin product.Specifically It says, it has been found that, the preparation of homogeneous mixture is difficult, moreover, heterogeneous polymeric blends are in the final product Application be not best.Therefore, this field ensures there is still a need for the homogeneous polyolefin product produced by polyvinyl resin and simultaneously The final product of low production cost and high-quality.
Invention content
Astoundingly, the inventors have discovered that improve polyethylene preparation method and overcome it is in the prior art it is above-mentioned and The mode of at least one of other problems.Therefore, the present invention relates to the preparation method of polyethylene product, the method includes with Lower step：
(a) the first polyvinyl resin, first polyethylene are produced in the reactor in the presence of a metallocene catalyst Resin has 0.940-0.970g/cm3Density and 0.01-300g/10 minutes MI2, wherein melt index (MI) MI2Pass through ASTM The program of D-1238 is measured using 190 DEG C of temperature and the load of 2.16kg；
(b) the second polyvinyl resin is individually produced in the reactor in the presence of Ziegler-Natta catalyst；With
(c) make described poly- to produce together with first polyvinyl resin and the second polyvinyl resin physical blending Ethylene product.
Preferably, it the present invention relates to the preparation method of polyethylene product, the described method comprises the following steps：
(a) the first polyvinyl resin, first polyethylene are produced in the reactor in the presence of a metallocene catalyst Resin has 0.940-0.970g/cm3Density and wherein described first polyvinyl resin have possess 2-250g/10 minutes MI2Low molecular weight (LMW), the density measures with ASTM D-1505 standardized tests at a temperature of 23 DEG C, melt index (MI) MI2It is measured using 190 DEG C of temperature and the load of 2.16kg by the program of ASTM D-1238；
(b) the second polyvinyl resin is individually produced in the reactor in the presence of Ziegler-Natta catalyst, wherein Second polyvinyl resin has the MI for possessing 0.01-15g/10 minutes2High molecular weight (HMW)；With
(c) make described poly- to produce together with first polyvinyl resin and the second polyvinyl resin physical blending Ethylene product.
It astoundingly, can the inventors have discovered that deriving from the polyvinyl resin of different catalysts by carefully selecting The polyethylene product of chemical stabilization and homogeneous is obtained by physical blending.In fact, according to the present invention, the catalysis of chemical incompatibility Agent combination can be combined astoundingly in physical blend.Astoundingly, the present invention cause better controlled process conditions, The polyethylene product of homogeneous and/or more preferably final product.The polyethylene product of the present invention is advantageously used for various applications.
Now, the invention will be further described.In the following paragraphs, different aspect of the invention is limited in more detail It is fixed.The various aspects so limited can be combined with any other aspect, unless clearly phase antirepresentation.Particularly, it is indicated as being preferably Or advantageous any feature can be combined with preferred or advantageous any other feature is indicated as being.
Specific implementation mode
Before this method used in describing the present invention, it should be appreciated that the present invention is not limited to specific method, the groups of description Point or device because such method, component and device can change certainly.It should also be understood that term used herein is not intended to To be restrictive, because the scope of the present invention is limited only by the appended claims.
Singulative " one (kind) (a, an) " as used herein and " being somebody's turn to do (described) " are comprising odd number and plural referents The two, unless in addition context clearly shows.
Term " comprising " used herein is synonymous with "comprising" or " containing " and is inclusiveness (inclusive) Or it is open and be not excluded for other, unrequited member, element or method and step.Term " comprising " is also covered by term " Consists of ".
By endpoint carry out numberical range enumerate all numbers included in respective range and part and Cited endpoint.
Term " about " used herein is worked as and is related to mensurable value such as parameter, amount, the sustained period of time Be intended to whens (temporal duration) etc. specified value and apart from specified value +/- 10% or less, preferably +/- 5% or Less, more preferably +/- 1% or less and the variation even more preferably from +/- 0.1%, so long as variation be suitable for disclosed It is carried out in invention.It should be understood that the value itself that modifier " about " is related to is also specific and preferably disclosed.
Unless otherwise defined, in the open present invention, used all terms (including technical and scientific term) have such as The normally understood meaning of those skilled in the art.By further guiding, including in specification The definition of term used is to more fully understand the teachings of the present invention.
In entire this specification, the embodiment party will be combined by referring to that " embodiment " or " embodiment " refer to Specific feature, the structure or characteristic of formula description are included at least one embodiment of the present invention.Therefore, in this entire theory Occur phrase " in one embodiment " at different location in bright book or is not necessarily all referring to " in embodiments " identical Embodiment, but it can refer to identical embodiment.In addition, as those skilled in the art will be apparent from present disclosure , in one or more embodiments, specific feature, structure or characteristic can combine in any suitable manner.Though in addition, Right some embodiments described herein include some features for including in other embodiment but do not include other implementations The other feature for including in mode, but as it will appreciated by a person of ordinary skill, the group of the feature of different embodiments is desirable Figure within the scope of the invention, and forms different embodiments.For example, in the following claims, arbitrary required guarantor The embodiment of shield can be used in any combination.
It is poly- second the present invention relates to the different polyvinyl resin physical blending of at least two will produced by different catalysts Ene product.Two kinds of resins preferably individually produce in separated reactor, preferably in separated circulation flow reactor, the circulation Reactor is preferably single loop reactor.
For the present invention, " villus (fluff) " is defined as in circulation flow reactor using hard catalyst granules at this The polymer material generated at the core of each particulate of powder.Term " resin " as used in this article covers in circulation flow reactor The villus produced and the polyethylene for then melting and/or pelletizing.For the present invention, " polyethylene product " or " poly- second Alkene pellet " is defined as through resin with the vinyl polymerization for mixing homogenizing (such as using mixing and/or extruder device) production Object material.
Astoundingly, the inventors have discovered that having 0.940-0.970g/cm3Density and 0.01-300g/10 point The MI of clock2The polyvinyl resin derived from metallocene can be with the polyethylene physical blending derived from ziegler-nata.The poly- second of the homogeneous Ene product then can be advantageously used in various applications.
Preferably, the first polyvinyl resin is produced in the reactor in the presence of a metallocene catalyst.Preferably, described First polyvinyl resin has 0.940-0.970g/cm3Density.Preferably, first polyvinyl resin has low molecule Measure (LMW) and more preferably with 2-250g/10 minutes MI2.In embodiments, first polyvinyl resin has single Peak is distributed.In another embodiment, first polyvinyl resin has bimodal molecular weight distribution.
Preferably, the second polyvinyl resin is produced in the reactor in the presence of Ziegler-Natta catalyst.Implementing In mode, second polyvinyl resin has the density equal to or less than first polyvinyl resin and more preferably has 0.920-0.960g/cm3Density.Preferably, second polyethylene has the MI for possessing 0.01-15g/10 minutes2High score Son amount (HMW).Preferably, second polyethylene has monomodal molecular weight distribution.
Preferably, at most 15 μm, more preferably up to 13 μm, most preferably up to 10 μm of average particle size (D50), most preferably extremely The second polyvinyl resin is produced in the presence of more 8 μm, such as at most 5 μm and preferably at least 3 μm of Ziegler-Natta catalyst.
D50 is defined as such granularity：For the granularity, the particle of 50 volume % has the size less than the D50.It can According to international standard ISO13320:2009("Particle size analysis-Laser diffraction methods") Carry out the measurement of average particle size (D50).For example, the laser diffraction system of Malvern Instruments is advantageously used.It can After supported catalyst is suspended in hexamethylene, surveyed by the laser diffraction analysis on Malvern type analysis instrument Measure D50.Suitable Malvern systems include Malvern2000, Malvern MasterSizer (such as Mastersizer S), Malvern2600 and Malvern3600 series.Such instrument and their operation manual meet or are even more than Listed requirement in ISO13320 standards.Malvern MasterSizer (such as Mastersizer S) or useful, Because by the theory of application Mie, using suitable optical instrument, it can more accurately measure the D50 towards range lower end, Such as the average particle size less than 8 μm.
So-called term " unimodal polymerisation object " or " polymer with monomodal molecular weight distribution " refer to, at them There are one the polymer of maximum value for tool referred to as in the molecular weight distribution curve of monomodal distribution curve.So-called term " has bimodal point The polymer of son amount distribution " or " bimodal polymers " refer to point with the summation for two monomodal molecular weight distribution curves The polymer of cloth curve.So-called term " polymer with multimodal molecular weight distribution " or " multimodal polymer ", refer to having For at least two, the polymer of the preferably greater than distribution curve of the summation of two monomodal distribution curves.So-called term " unimodal poly- second Alkene " or " polyethylene with monomodal molecular weight distribution " refer to, in the molecular weight point of their also referred to as monomodal distribution curve There are one the polyethylene of maximum value for tool in cloth curve.So-called term " polyethylene with multimodal molecular weight distribution " or " multimodal is poly- Ethylene product " refers to, has at least two, preferably greater than the distribution curve of the summation of two monomodal distribution curves is poly- Ethylene.
Preferably, it is polyethylene product by at least two polyvinyl resins physical blending.Preferably, of the invention poly- Ethylene product has 0.920-0.960g/cm3Density.Preferably, polyethylene product of the invention has 0.01-100g/10 The MI of minute2.In embodiments, the polyethylene product has monomodal molecular weight distribution.In another embodiment, described Polyethylene product is distributed with multimodal molecular weight.
To measure MI using the ASTM D-1238 standardized tests of 190 DEG C of temperature and the load of 2.16kg2.With ASTM D-1505 standardized tests measure density at a temperature of 23 DEG C.
Preferably, weight of first polyvinyl resin in the polyethylene product to second polyvinyl resin Amount is than being 0.20-5.Preferably, the polyethylene product includes at least 10 weight %, more preferably at least 25 weight %, most preferably extremely The first polyethylene tree of few 40 weight % and at most 90 weight %, more preferably up to 75 weight %, most preferably up to 60 weight % Fat, the total weight based on the polyethylene product.Preferably, the polyethylene product includes at least 10 weight %, more preferably at least 25 weight %, most preferably at least 40 weight % and at most 90 weight %, more preferably up to 75 weight %, most preferably up to 60 weight %'s Second polyvinyl resin, the total weight based on the polyethylene product.Preferably, the multimodal polyethylene product includes extremely Few 10 weight %, more preferably at least 25 weight %, most preferably at least 40 weight % and at most 90 weight %, more preferably up to 75 weight %, Most preferably up to first polyvinyl resin of 60 weight %, and it is at least 10 weight %, more preferably at least 25 weight %, optimal Select the described second poly- second of at least 40 weight % and at most 90 weight %, more preferably up to 75 weight %, most preferably up to 60 weight % Olefine resin, the total weight based on the polyethylene product.
Preferably, in by described two polyvinyl resin physical blendings to the equipment for melting and being blended the resin, The equipment is selected from mixing machine, extruder or combination thereof.For example, the equipment is extruder and/or mixing machine.It is preferred that Ground, the equipment are extruder.Preferred extruder is co-rotating twin screw.Preferred mixing machine is to reversely rotate double spiral shells Bar.
Present invention encompasses be used to prepare polyvinyl resin.Polyvinyl resin is preferably in the reactor in the gas phase Or it prepares under slurry conditions.Preferably, the polyethylene is prepared under slurry conditions.It is highly preferred that the polyethylene exists It is produced in circulation flow reactor, the circulation flow reactor preferably includes the interconnecting tube in defined reaction device path, and wherein will preferably become silted up Stock pump is sent through the circulation flow reactor.Preferably, it is produced respectively in single loop reactor every in the polyvinyl resin It is a kind of.In embodiments, it can be produced in the double loop reactor for the circulation flow reactor being connected in series with including two described poly- Each in vinyl.
As used in this article, term " polymerisation slurry " or " polymer slurries " or " slurry " substantially refer to including at least poly- The heterogeneous compositions of object solid and liquid phase are closed, which is continuous phase.Solid includes catalyst and the alkene such as polyethylene of polymerization. Liquid includes monomer such as ethylene, comonomer, the molecular weight regulator such as hydrogen, anti-quiet of inert diluent such as iso-butane, dissolving Electric agent, scale preventative, scavenger and other processing aids.
Term " metallocene catalyst " is used for describing the metallic atom group by being bound to one or more ligands herein At any transition metal complex.The metallocene catalyst is periodic table group iv transition metals such as titanium, zirconium, hafnium Compound, and have and possess metallic compound and by one kind or two in cyclopentadienyl group, indenyl, fluorenyl or their derivative The coordination structure for the ligand that kind group is constituted.Metallocene catalyst is used to have the advantages that in the polymerization of alkene various.Metallocene Catalyst is with high activity and can prepare the polymer with the physical property enhanced.The key of metallocene is complex compound Structure.Depending on desired polymer, the structure and geometrical condition (geometry) of changeable metallocene are to adapt to the producer's It is specific to need.Metallocene includes monometallic center, allows more controls of the branched and molecular weight distribution for polymer.It is single Between body is inserted into metal and the polymer chain that grows.
In a preferred embodiment, metallocene catalyst has logical formula (I) or (II)：
(Ar)2MQ2(I)；Or
R”(Ar)2MQ2(II)
Wherein it is non-bridged combined metal according to the metallocene of formula (I) and is bridged combined metal according to the metallocene of formula (II)；
Wherein had according to the metallocene of formula (I) or (II) and is attached to two Ar of M, it can be mutually the same or not Together；
Wherein Ar be aromatic ring, group or part and wherein each Ar independently selected from cyclopentadienyl group, indenyl (IND), Tetrahydro indenyl (THI) or fluorenyl, wherein the group respectively optionally by one or more be each independently selected from it is following Substituent group replaces：Halogen, hydrosilane groups (hydrosilyl), the SiR that wherein R is the alkyl with 1~20 carbon atom3Base Group and the alkyl with 1~20 carbon atom, and the wherein described alkyl includes optionally B, Si, S, O, F, Cl containing being selected from With one or more atoms of the group of P；
Wherein M is the transition metal selected from titanium, zirconium, hafnium and vanadium；And preferably zirconium；
Wherein each Q is independently selected from halogen；Oxyl (hydrocarboxy) with 1~20 carbon atom；And tool There is the alkyl of 1~20 carbon atom, and the wherein described alkyl optionally contains selected from the group for including B, Si, S, O, F, Cl and P One or more atoms；With
Wherein R ' ' be two Ar groups of bridging bivalent group or part and be selected from C1-C20Alkylidene, germanium, silicon, silica Alkane, alkylphosphines and amine, and the wherein described R ' ' is optionally each independently selected from following substituent group by one or more and replaces： Halogen, hydrosilane groups, the SiR that wherein R is the alkyl with 1~20 carbon atom3Group and with 1~20 carbon atom Alkyl, and the wherein described alkyl optionally contains one or more atoms selected from the group for including B, Si, S, O, F, Cl and P.
Term " alkyl with 1-20 carbon atom " used herein is intended to refer to selected from the part for including following group： Line style or branched C1-C20Alkyl, C3-C20Naphthenic base, C6-C20Aryl, C7-C20Alkaryl and C7-C20Aralkyl or they Arbitrary combination.Illustrative alkyl be methyl, ethyl, propyl, butyl, amyl, isopentyl, hexyl, isobutyl group, heptyl, octyl, Nonyl, decyl, cetyl, 2- ethylhexyls and phenyl.Illustrative halogen atom includes chlorine, bromine, fluorine and iodine and at this In a little halogen atoms, fluorine and chlorine are preferred.The example of alkylidene is methylene, ethylidene and propylidene.
Preferred metallocene catalysed agent for producing first polyvinyl resin is selected from general formula (IndH4) 2R4MQ2It is double Tetrahydro indenyl compound, wherein each Ind is identical or different and is indenyl or substituted indenyl, R4It includes C to be1-20Alkylidene, dioxane The bridge of base germanium or silicon or siloxanes or alkylphosphines or amine groups, the bridge are substituted or unsubstituted, and M is Group IVB transition gold Belong to or vanadium and each Q are the alkyl or halogen for having 1-20 carbon atom.
The illustrative example of metallocene catalyst includes but not limited to bis- (cyclopentadienyl group) zirconium dichloride (Cp2ZrCl2)、 Bis- (cyclopentadienyl group) titanium chloride (Cp2TiCl2), bis- (cyclopentadienyl group) hafnium dichloride (Cp2HfCl2)；Bis- (tetrahydro indenyls) Zirconium dichloride, bis- (indenyl) zirconium dichlorides and bis- (normal-butyl-cyclopentadienyl group) zirconium dichlorides；Ethylenebis (4,5,6,7- tetra- Hydrogen -1- indenyls) zirconium dichloride, ethylenebis (l- indenyls) zirconium dichloride, bis- (the 2- methyl 4-phenyls-of dimethylated methylene silylation Indenes -1- bases) zirconium dichloride, diphenylmethylene (cyclopentadienyl group) (fluorenes -9- bases) zirconium dichloride and dimethylated methylene base [1- (4- tertiary butyl -2- methyl-cyclopentad ienyls)] (fluorenes -9- bases) zirconium dichloride.
In general, metallocene catalyst is provided on a solid carrier.The carrier should be inert solid, with conventional cyclopentadienyl The arbitrary component of metallic catalyst does not have chemical reactivity.The carrier is preferably silicon dioxide compound.Preferred real It applies in mode, metallocene catalyst is provided on solid carrier, preferably silica supports.
The term " Ziegler-Natta catalyst " or " ZN catalyst " refer to formula M1XvCatalyst, wherein M1 It is the transistion metal compound selected from Group IV-Section VII race, wherein X is halogen, and the chemical valence that wherein v is the metal.It is excellent Selection of land, M1It is Group IV, group V or group vi metal, more preferably titanium, chromium or vanadium, and most preferably titanium.Preferably, X is chlorine Or bromine, and most preferably chlorine.The illustrative example of the transistion metal compound includes but not limited to TiCl3、TiCl4.For this The suitable ZN catalyst of invention describes in US6930071 and US6864207, introduces them into herein as reference.
It is comprising neat for the present invention, the particularly a preferred catalyst in particular for producing second polyvinyl resin The ziegler-natta catalyst systems of Ge Le-Natta catalyst components D and pre-activate agent, wherein the ziegler-natta catalyzed Agent component D can be by obtaining as follows：
A) by making magnesium diaikoxide compound produce reaction product A with halogenating agent；
B) reaction product A is made to be contacted with the first halogenation/titanizing (titanating) agent to form reaction product B；
C) reaction product B is made to be contacted with the second halogenation/titanizing agent to form reaction product C；With
D) reaction product C is made to be contacted with third halogenation/titanizing agent to form catalytic component D.
Preferably, the catalyst is manufactured according to the method included the following steps：A) make magnesium diaikoxide compound and halogen Agent is contacted to form reaction product A；B) reaction product A is made to be contacted with the first halogenation/titanizing agent to form reaction product B；c) Reaction product B is set to be contacted with the second halogenation/titanizing agent to form reaction product C；And d) make reaction product C and third halogenation/titanium Agent is contacted to form reaction product D.Described second and third halogenation/titanizing agent may include titanium tetrachloride.Second and third halogen Change/titanation step can include respectively titanium within the scope of about 0.1-5 to the ratio between magnesium.Reaction product A, B and C can each leisure it is subsequent It is washed with hydrocarbon solvent before halogenation/titanation step.The reaction product D can be washed with hydrocarbon solvent until titanium substance [Ti] content is small In about 100mmol/L.
In embodiments, the method for manufacturing catalytic component generally includes following steps：By metal diaikyl and Alcohol forms metal diaikoxide, metal diaikoxide described in halogenation to form reaction product, make the reaction product at three or Contacted with one or more halogenations/titanizing agent in more steps to form catalytic component, and then use pre-activate agent if any The machine aluminium processing catalytic component.
Manufacturing an embodiment of the method for catalyst can be generally as follows：
1.M1RR'+2R"OH→M1(OR")2
2.M1(OR")2+ClAR"'x→"A”
3."A”+TiCl4/Ti(OR"")4→"B”
4."B”+TiCl4→"C"；
5."C”+TiCl4→"D”
6. " D "+pre-activate agent → catalyst
In above formula, M1Can be any suitable metal, usually group iia metal, typically Mg.In above formula, R, R', R'', R''' and R'''' are each independently alkyl or substituted hydrocarbon radical part, and R and R' has 1-20 carbon atom, leads to Normal 1-10 carbon atom, typically 2-6 carbon atom, and can have 2-4 carbon atom.R'' generally comprises 3-20 carbon atom, R''' generally comprises 2-6 carbon atom and R'''' generally comprises 2-6 carbon atom and typically butyl.Usable R, R', The arbitrary combination of two or more in R'', R''' and R'''', but can be identical or R group combination that This is different.
Including formula ClAR'''xEmbodiment of above in, A be can change a chlorine into alkoxy (alkoxide) Irreducibility (non-reducing) oxyphie (oxyphilic) compound, R''' is alkyl or substituted hydrocarbon radical and the change that x is A Conjunction valence subtracts 1.The example of A includes titanium, silicon, aluminium, carbon, tin and germanium, typically titanium or silicon, and wherein x is 3.The example packet of R''' Include methyl, ethyl, propyl, isopropyl and the similar group with 2-6 carbon atom.The chlorinating agent that can be used in the method Non-limiting examples be ClTi (OiPr)3With ClSi (Me)3。
By the metal diaikoxide chlorination of embodiment of above to form reaction product " A "." accurate group of A " although product At being unknown, but think the metallic compound it includes partial oxidation, a reality of the metallic compound of the partial oxidation Example can be ClMg (OR'').
Then make reaction product " A " and one or more halogenations/titanizing agent such as TiCl4With Ti (OBu)4Combination contact, To form reaction product " B "." B " may be the metal of chlorination and partial oxidation and the complex compound of titanium compound to reaction product.Instead Answering product, " B " may include the MgCl of titanium dipping2Carrier and for example can be by compound such as (MCl2)y(TiClx(OR)4-x)zIt indicates.Instead Answering product, " B " can be precipitated from the catalyst slurry in solid form.
" C " may also be halogenation and partially halogenated for second halogenation/titanation step production reaction product or catalytic component Metal and titanium compound complex compound but different from " B ", and can be by (MCl2)y(TiClx'(OR)4-x')z'It indicates.It is expected that " C " Halogenation level be more than product " halogenation of B " be horizontal.The halogenation level of the bigger can produce the different complexes of compound.
" D " may also be halogenation and partially halogenated for third halogenation/titanation step production reaction product or catalytic component Metal and titanium compound complex compound but different from " B " and " C ", and can be by (MCl2)y(TiClx"(OR)4-x")z"It indicates.In advance The halogenation for counting " the halogenation level of D " is greater than product " C " is horizontal.The different complexings of the halogenation level production compound of the bigger Object.Although to the reaction product, this description provides currently to the most probable explanation of chemical property, the method is not It is limited by the theoretical mechanism.
Suitable in the method metal diaikyl and gained metal diaikoxide may include can be used in the side To produce the arbitrary metal diaikyl and metal diaikoxide of suitable polyethylene catalysts in method.These metal diaikoxides and Metal diaikyl may include the diaikoxide and alkylated material of group iia metal.The metal diaikoxide or dioxane Base Metal can be dialkoxy magnesium or dialkyl magnesium.The non-limiting examples of suitable dialkyl magnesium include magnesium ethide, dipropyl Base magnesium, dibutylmagnesium, butyl ethyl magnesium etc..Butyl ethyl magnesium (BEM) is a kind of suitable dialkyl magnesium.
In the practice of the method, the metal diaikoxide can be formula M g (OR ")2Magnesium compound, wherein R'' For the alkyl or substituted hydrocarbon radical of 1-20 carbon atom.
The metal diaikoxide can be soluble and typically irreducibility.Irreducibility compound has such as Lower advantage：Form MgCl2Rather than the insoluble substance that can be formed by the reduction of compound such as MgRR', this can cause to have The formation of the catalyst of wide size distribution.In addition, reactivity is less than the Mg (OR ") of MgRR'2When for being related to mild chlorine Agent implements chlorination can lead to product evenly, such as preferably when being the reaction of subsequent halogenation/titanation step later Catalyst grain size controls and distribution.
The non-limiting examples of workable metal diaikoxide substance include butanol magnesium, amylalcohol magnesium, hexanol magnesium, two (2- Ethyl hexanol) magnesium and it is suitable for making the soluble any alcoxylates of the system.
As non-limiting examples, dialkoxy magnesium such as two (2-Ethylhexyl Alcohol) magnesium can be by making alkyl magnesium compound (MgRR') it reacts and manufactures with alcohol (ROH), as follows.MgRR'+2R"OH→Mg(OR")2+RH+R'H。
The reaction can carry out at room temperature and reactant forms solution.R and R' can be respectively times of 1-10 carbon atom What alkyl, and may be the same or different.Suitable MgRR' compounds include such as magnesium ethide, dipropyl magnesium, dibutylmagnesium and fourth Base magnesium ethide.The MgRR' compounds can be that BEM, wherein RH and R'H are respectively butane and ethane.
In the practice of the method, any alcohol for generating desired metal diaikoxide can be used.In general, the alcohol used Can be general formula R ' ' any alcohol of OH, wherein R'' is the alkyl of 2-20 carbon atom, carbon atom can at least three, at least four, At least five or at least six carbon atom.The non-limiting examples of suitable alcohols include ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, 2- methyl anyl alcohols, 2-Ethylhexyl Alcohol etc..Although it is considered that almost arbitrary alcohol can be used, but line style or branched, higher can be used The branching alcohol of grade, such as 2- ethyl -1- hexanols.
The amount for the alcohol being added can for example become in (non-exclusive) range for being not excluded for endpoint of 0-10 equivalents Change, usually in the equivalent weight range of about 0.5 equivalent-about 6 (equivalent is relative to whole metallic compounds or magnesium), and can about 1- about In 3 equivalent weight ranges.
Alkyl metal cpd can lead to high molecular weight material very viscous in the solution.It can be by being added into reaction The alkyl aluminum such as triethyl aluminum (TEAl) of the intermolecular association of individual metal alkyl can be destroyed to reduce the high viscosity.Alkyl The typical proportions of aluminium and metal can be 0.001:1-1:1, can be 0.01-0.5:1, and can also be 0.03:1-0.2:1.In addition, It can be used electron donor such as ether such as diisoamyl ether (DIAE) to further decrease the viscosity of the metal alkyl.Electron donor With the typical proportions ranging from 0 of metal:1-10:1, and can ranging from 0.1:1-1:1.
Described in halogenation the step of metal alkoxides in useful reagent will generate conjunction when including in for the method Any halogenating agent of suitable polyethylene catalysts.The halogenation step can be that the wherein described halogenating agent includes chlorine (being chlorinating agent) Chlorinating step.
The halogenation of the alkoxide compound is implemented usually in hydrocarbon solvent under inert atmosphere.Suitable solvent it is non- Limitative examples include toluene, heptane, hexane, octane etc..In the halogenation step, the molar ratio of metal alkoxides and halogenating agent Usually about 6:1- about 1:It, can be about 3 in the range of 3:1- about 1:It, can be about 2 in the range of 2:1- about 1:In the range of 2, and It also can be about 1:1.
The halogenation step is usually implemented at a temperature in the range of about 0 DEG C-about 100 DEG C and carries out about 0.5- about 24 hours Reaction time in range.The halogenation step can be implemented at a temperature in the range of about 20 DEG C-about 90 DEG C and to carry out about 1 small When-about 4 hours within the scope of reaction time.
Once implementing the halogenation step and the metal alkoxides being by halogenation, so that it may to halide product " A " into Row halogenation/titanizing processing two or more times.
Used halogenation/titanizing agent can be the blend of two kind of four substitution titanium compound, wherein four all substitutions Base is identical and substituent group is halogen or alkoxy or phenolic group with 2-10 carbon atom, the titanium compound such as TiCl4 Or Ti (OR " ")4.Used halogenation/titanizing agent can be chlorination/titanizing agent.
The halogenation/titanizing agent can be the combination of single compound or compound.The method the first halogenation/titanizing it After active catalyst is provided；At least three halogenations/titanation step is amounted to however, it is expected that existing.
First halogenation/titanizing agent is typically mild titanizing agent, can be being total to for halogenated titanium and organic titanate Mixed object.First halogenation/titanizing agent can be TiCl4With Ti (OBu)40.5:1-6:1 TiCl4/Ti(OBu)4In range Blend, the ratio can be 2:1-3:1 (" OBu " represents butoxy).Think that the blend of halogenated titanium and organic titanate is anti- It should be to form alkoxy titanium Ti (OR)aXb, wherein OR and X are respectively alkoxy and halogen and the chemical valence that a+b is titanium, Typically 4.
In alternative solution, first halogenation/titanizing agent can be single compound.The example of first halogenation/titanizing agent For Ti (OC2H5)3Cl、Ti(OC2H5)2Cl2、Ti(OC3H7)2Cl2、Ti(OC3H7)3Cl、Ti(OC4H9)Cl3、Ti(OC6H13)2Cl2、 Ti(OC2H5)2Br2With Ti (OC12H5)Cl3。
First halogenation/titanation step is usually by the way that in room temperature/environment temperature, by the halogenated products, " A " is in hydrocarbon first It carries out slurried in solvent and implements.The non-limiting examples of suitable hydrocarbon solvent include heptane, hexane, toluene, octane etc..Institute Stating product, " it is at least partially soluble solution that A ", which can be in the hydrocarbon solvent,.
It is added in solid product " B " to soluble product " A " after halogenation/titanizing agent and precipitates at room temperature. The amount of used halogenation/titanizing agent must be enough to be settled out solid product from solution.Generally, based on the ratio of titanium and metal Example, the amount of halogenation used/titanizing agent is usually in the range of about 5 about 0.5-, typically in the range of about 4 about 1-, and It can be in the range of about 2.5 about 1.5-.One example is TiCl4/ butanol titanium (IV) (TNBT).
The solid product that is precipitated in first halogenation/titanation step " B " and then is received by any suitable technology of collecting It takes, is then washed with solvent such as hexane in room temperature/environment temperature.In general, washing the solid product, " B " is until [Ti] is small In about 100mmol/L.In the method, [Ti] indicates to potentially act as any titanium substance of second generation Ziegler catalyst, Including the titanium substance not as a part for reaction product as described herein.Then by products therefrom, " B " carries out the second He Third halogenation/titanation step is to manufacture product " C " and " D ".After each halogenation/titanation step, washable solid product is straight It is less than desired amount to [Ti].For example, less than about 100mmol/L, being less than about 50mmol/L or being less than about 10mmol/L. After final halogenation/titanation step, washable product is until [Ti] is less than desired amount.For example, being less than about 20mmol/ L, it is less than about 10mmol/L or is less than about 1.0mmol/L.Think that lower [Ti] can may act as second generation Ziegler by reducing The amount of the titanium of substance and generate improved catalyst result.Think that lower [Ti] can be to generate improved catalyst result such as A factor in narrower MWD.
Second halogenation/titanation step usually by solid product that will be collected from the first titanation step (solid product " B ") it is slurried in hydrocarbon solvent and implement.It is usable molten as the hydrocarbon for being suitable for first halogenation/titanation step and listing Agent.Described second and third halogenation/titanation step can be used different from first halogenation/titanation step compound or chemical combination The combination of object.Described second and third halogenation/titanation step concentration can be used to be better than to use in first halogenation/titanizing agent The identical reagent of concentration, but this is not necessary.Described second and third halogenation/titanizing agent can be halogenated titanium such as titanium tetrachloride (TiCl4).The halogenation/titanizing agent is added in slurry.The addition can be carried out in environment/room temperature, but also can be in difference It is carried out at the temperature and pressure of environment.
In general, described second and third halogenation/titanizing agent include titanium tetrachloride.Typically, second and third halogenation/titanizing Step includes respectively titanium/magnesium ratio within the scope of about 0.1-5, it is possible to use about 2.0 ratio, and about 1.0 ratio can be used. Third halogenation/the titanation step usually carries out at room temperature and in slurry, but also can be in the temperature and pressure different from environment It is carried out under power.
Used titanium tetrachloride or the amount of halogenation/titanizing agent can indicate that equivalent here is that titanium is opposite with equivalent In the amount of magnesium or metallic compound.Second and third halogenation/respective titanium of titanation step amount usually in about 5.0 equivalents of about 0.1- In the range of, it can typically expect with it in the range of about 0.3- about 3 equivalents in the range of about 0.25- about 4 equivalents Ground is in the range of about 0.4- about 2.0 equivalents.In a specific embodiment, in second and third halogenation/titanation step The amount of the titanium tetrachloride used in each is in the range of about 0.45- about 1.5 equivalents.
" D " can be with organometallic catalyst component (" pre-activate agent ") group for the catalytic component manufactured by the above method It closes, to form the preactivated catalyst system for being suitable for olefinic polymerization.Typically, with catalytic component comprising transition metal " The pre-activate agent that D " is used together is organo-metallic compound such as alkyl aluminum, alkyl-al hydride, alkyl aluminum lithium, zinc alkyl, alkyl Magnesium etc..Preferably, the pre-activate agent is selected from trialkylaluminium, dialkylaluminum halides and alkyl dihalides aluminium.
The pre-activate agent is preferably organo-aluminum compound.The organo-aluminium pre-activate agent is typically formula AlR3Alkyl Aluminium, wherein at least one R is alkyl or halogen with 1-8 carbon atom, and wherein each R may be the same or different.Suitably Pre-activate agent includes trialkylaluminium such as trimethyl aluminium (TMA), triethyl aluminum (TEAL), triisobutyl aluminium (TIBAL) and also wraps Include diethyl aluminum chloride, triisobutyl aluminium chloride, buty laluminum dichloride etc. and their mixture.The pre- work of organo-aluminium Agent is more preferably trimethyl aluminium (TMA), triethyl aluminum (TEAL), triisobutyl aluminium (TIBAL) or their mixture.It is excellent Selection of land, the pre-activate agent is TEAL, because using TEAL, the molecular weight point of the polyethylene prepared in two tandem reactors Cloth (MWD) is more even broader than when using other organo-aluminium pre-activate agent.In general, when using TEAL as pre-activate agent, MWD It is at least 5, preferably at least 6.
In general, the ratio of Al and titanium can be 0.1:1-2:In the range of 1 and typically 0.25:1-1.2:1.
It optionally, can be by the Ziegler-Natta catalyst prepolymerization.In general, prepolymerization method by catalyst So that a small amount of monomer is contacted with catalyst after being contacted with pre-activate agent and implement.Prepolymerization method description U.S5,106,804, In 5,153,158 and 5,594,071, introduce them into herein as reference.
It optionally, can be by electron donor and the halogenating agent, the first halogenation/titanizing agent or subsequent one or more halogen Change/titanizing agent is added together.It can be desired that electron donor is used in second halogenation/titanation step.For polyethylene The electron donor of catalyst preparation is well known, and can be in the method using will provide any suitable of suitable catalyst Electron donor.Electron donor (also referred to as Louis (Lewis) alkali) be the oxygen that electronics pair can be provided to catalyst, nitrogen, phosphorus or The organic compound of sulphur.
Electron donor can be simple function or polyfunctional compound, can be selected from aliphatic series or aromatic carboxylic acid and they Arrcostab, Aliphatic series or cricoid ether, ketone, vinyl esters, acryl derivatives especially alkyl acrylate or methacrylate Ester and silane.The example of suitable electron donor is n-butyl phthalate.The general example of suitable electron donor It is general formula R Si (OR')3Alkyl alkoxy monosilane, such as methyl-triethoxysilane [MeSi (OEt)3], wherein R and R' For the alkyl with 1-5 carbon atom, and it may be the same or different (" OEt " expression " ethyoxyl ").
For the polymerization, can be used using internal electron donor and in polymerization in the synthesis of the catalyst External electron donor or stereoselectivity control agent (SCA) activate the catalyst.It can be in the formation of catalyst reaction in halogen Internal electron donor is used during change or halogenation/titanation step.It is suitable as being used to prepare conventional load Ziegler-Natta catalyst The compound of the internal electron donor of component includes ether, diether, ketone, lactone, the electron donor chemical combination with N, P and/or S atom Object and particular kind of ester.It is particularly suitable to the ester of phthalic acid, such as diisobutyl phthalate, O-phthalic Dioctyl phthalate, diphenyl phthalate and benzyl butyl phthalate；The ester of malonic acid, such as malonic acid diisobutyl ester and Diethyl malonate；New pentane acid alkyl ester and neopentanoic acid aryl ester；Alkyl maleates, maleic acid cycloalkyl ester and maleic acid virtue Base ester；Alkyl carbonate and aryl carbonates such as carbonic acid diisobutyl ester, carbonic acid Ethyl-phenyl ester and diphenyl carbonate；Succinic acid Ester such as diethyl succinate and diethyl succinate.
The external donor that can be used in the preparation of catalyst includes organic silane compound such as general formula SiRm(OR')4-mAlcoxyl Base silane, wherein R are selected from alkyl, naphthenic base, aryl and vinyl；R' is alkyl；It is 0-3 with m, wherein R can be identical as R'；When When m is 0,1 or 2, R' groups may be the same or different；With when m is 2 or 3, R group may be the same or different.
The external donor of the method can be selected from the silane compound of following formula：Wherein R1And R4Be comprising be connected to silicon primary, Secondary or tertiary carbon atom alkyl or cycloalkyl, R1And R4It is identical or different；R2And R3For alkyl or aryl.R1Can be methyl, isopropyl Base, cyclopenta, cyclohexyl or tertiary butyl；R2And R3It can be methyl, ethyl, propyl or butyl and be not required identical；And R4Also may be used For methyl, isopropyl, cyclopenta, cyclohexyl or tertiary butyl.Specific external donor is Cyclohexyl Methyl Dimethoxysilane (CMDS), diisopropyl dimethoxy silane (DIDS), cyclohexyl isopropyl dimethoxysilane (CIDS), bicyclopentyl diformazan Oxysilane (CPDS) or di-t-butyl dimethoxysilane (DTDS).
Preferably, the pre-activate agent is organo-aluminum compound, preferably has formula AlR3, wherein R is former with 1-8 carbon The alkyl or halogen of son, and wherein each R may be the same or different.It is highly preferred that the organo-aluminum compound is TEAL.
Preferably, the halogenating agent is ClTi (OPr)3.Preferably, first halogenation/titanizing agent is TiCl4And Ti (OBu)40.5:1-6:1 TiCl4/Ti(OBu)4Mixture in molar ratio range.It is further preferred that the molar ratio is 2:1 TiCl4/Ti(OBu)4.Preferably, second halogenation/titanizing agent is TiCl4.Preferably, the third halogenation/titanizing agent It is TiCl4。
According to embodiment, the Ziegler-Natta catalyst for producing second polyvinyl resin has at most 15 μ The average particle size (D50) of m, wherein D50 is measured by the laser diffraction analysis on Malvern type analysis instrument.
Can as described earlier in this article as prepare at most 15 μm average particle sizes (D50) ziegler-natta catalyzed Agent.Average particle size (D50) at most 15 μm of other suitable Ziegler-Natta catalyst can be obtained from Lyondellbasell is purchased in market Or from W.R.Grace and Company acquisitions purchased in market, such as with 10 μm of average particle sizes5910。
It is preferred that being added to catalyst as catalyst slurry in circulation flow reactor.As used in this article, term " catalysis Agent slurry " refers to the composition for including catalyst solid particle and diluent.The solid particle can be spontaneously or by all It is suspended in diluent such as mixed homogenizing technology.The solid particle, which can be non-uniformly distributed in diluent and be formed, to sink Starch or deposit.
Optionally, activator is used during according to the present invention.Term " activator " refers to that can be combined with catalyst Using to improve the material of the catalyst activity in polymerization process.In the present invention, it particularly relates to such organo-aluminium Compound：It optionally by halogenation, has general formula AlR11R12R13Or AlR11R12Y, wherein R11、R12、R13It is with 1-6 carbon The alkyl of atom, and R11、R12、R13It may be the same or different, and wherein Y is hydrogen or halogen, such as US6930071 and US6864207 Disclosed in (introducing them into herein as reference).Preferred activator is triethyl aluminum (TEAl), triisobutyl aluminium (TIBAl), trimethyl aluminium (TMA) and methyl-methyl-ethyl aluminium (MMEAl).TEAl is particularly preferred.In embodiments, Activator is in the concentration less than 90 weight % of activator slurry composition, more preferable 10-50 weight %, for example, about 20 weight % Under activator slurry be added in circulation flow reactor.Preferably, the concentration of activator is less than 200ppm in circulation flow reactor, more It is preferred that 10-100ppm, most preferably 20-70ppm, and for example, about 50ppm.
As used in this article, term " monomer " refers to olefin(e) compound to be polymerized.The example of olefinic monomer is ethylene And propylene.Preferably, the present invention is directed to ethylene.
As used in this article, term " diluent " refers in liquid, is at room temperature liquid and preferably anti-in circulation Answer the diluent for liquid under the pressure condition in device.It is suitble to diluent used according to the invention to may include but be not limited to hydrocarbon dilute Release agent such as aliphatic series, the halogenated form of alicyclic solvents and aromatic hydrocarbon solvent or such solvent.Preferred solvent be C12 with Under, linear or branched saturated hydrocarbon；C5-C9's is saturated alicyclic or aromatic hydrocarbon or the halogenated hydrocarbons of C2-C6.The non-limit of solvent The illustrative example of property processed be butane, iso-butane, pentane, hexane, heptane, pentamethylene, hexamethylene, cycloheptane, methyl cyclopentane, Hexahydrotoluene, isooctane, benzene,toluene,xylene, chloroform, chlorobenzene, tetrachloro-ethylene, dichloroethanes and trichloroethanes.In this hair In bright preferred embodiment, the solvent is iso-butane.However, by the present invention it should be clear that can also be answered according to the present invention With other diluents.
Suitable vinyl polymerization includes but not limited to that the homopolymerization of ethylene, ethylene are total to more advanced 1- olefin comonomers It is poly-.
As used in this article, term " comonomer " refers to suitable for the olefin-copolymerization list with vinyl monomer polymerization Body.Comonomer may include but be not limited to the alpha-olefin of aliphatic C3-C20.The example packet of the alpha-olefin of aliphatic series C3-C20 appropriate Include propylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- octenes, 1- decene, 1- dodecylenes, 14 carbon of 1- Alkene, cetene, 1- octadecenes and 1- eicosylenes.Term " copolymer " refers to by being connected in same polymer chain Prepared by two kinds of different types polymer.Term " homopolymer " refers to passing through connection there is no comonomer Prepared by vinyl monomer polymer.In embodiments of the present invention, the comonomer is 1- hexenes.
In a preferred embodiment, single using the iso-butane including monomer ethylene, as hydrocarbon diluent, catalyst, copolymerization The reactant of body 1- hexenes.
The polymerization can carry out over a wide temperature range.Preferably, range of the temperature at about 0 DEG C to about 110 DEG C It is interior.It is ranging from about 60 DEG C to about 100 DEG C, more preferably from about 80 to 110 DEG C preferred.
Reaction pressure is preferably maintained at 20-100 bars, 30-50 bars, is more preferably under 37-45 bars of pressure.In embodiment party In formula, slurry flow rate may be set to 5-15m/s.
The warp of the present invention can be readily produced under flexible processing conditions by using the first polyethylene product of granulation The polyethylene product of granulation also results in the polyethylene product through granulation of homogeneous.The method provides a variety of advantages, such as It is easy to process.
Following non-limiting embodiment illustrates the present invention.
Embodiment
By by the first polyethylene fluff with monomodal molecular weight distribution and with 0.942Kg/l density of 25 weight % It melts and is blended together with the second polyethylene fluff physics with monomodal molecular weight distribution of 75 weight % to produce polyethylene Resin.
Produce first polyethylene fluff in the presence of a metallocene catalyst in single loop reactor.In monocycle stream Second polyethylene fluff is produced in reactor in the presence of Ziegler-Natta catalyst.The characteristic of the villus produced It is listed in Table 1 below.
Table 1
Characteristic First PE villus 2nd PE villus
Catalyst used Metallocene Ziegler-nata
MI2G/10 minutes 2 2
Cashmere density Kg/l 0.942 0.960
According to ASTM D-1238 MI is measured under 190 DEG C, 2.16kg loads2。
The extrusion of the blend is carried out in Total Petrochemicals Antwerp.The characteristic of the blend It is listed in Table 2 below with property.The characteristic and property of comparative example are also shown in Table 2 below.
Table 2
As shown in table 2, blend according to the present invention has than depositing in metallocene or Ziegler-Natta catalyst In the high stress cracking resistance of the multimodal polyethylene resin of lower production.

Claims (12)

1. the preparation method of polyethylene product, described method includes following steps：
(a) the first polyvinyl resin, first polyvinyl resin are produced in the reactor in the presence of a metallocene catalyst With 0.942-0.970g/cm3Density and wherein described first polyvinyl resin have and possess 2-250g/10 minutes MI2's Low molecular weight (LMW), the density are measured with ASTM D-1505 standardized tests at a temperature of 23 DEG C, the melt index (MI) MI2It is measured using 190 DEG C of temperature and the load of 2.16kg by the program of ASTM D-1238；
(b) the second polyvinyl resin is individually produced in the reactor in the presence of Ziegler-Natta catalyst, wherein described Second polyvinyl resin has the MI for possessing 0.01-15g/10 minutes2High molecular weight (HMW)；With
(c) make together with first polyvinyl resin and the second polyvinyl resin physical blending to produce the polyethylene Product；
First polyvinyl resin in the wherein described polyethylene product is to the weight ratio of second polyvinyl resin 0.20-5。
2. the method for claim 1 wherein the metallocene catalyst for producing first polyvinyl resin includes logical Formula (IndH4) 2R4MQ2Double tetrahydro indenyl compounds, wherein each Ind it is identical or different and be indenyl or substituted indenyl, R4For Including C1-20The bridge of alkylidene, dialkyl Germanium or silicon or siloxanes or alkylphosphines or amine groups, the bridge are substitutions or do not take Generation, M, which is Group IVB transition metal or vanadium, and each Q is has the alkyl or halogen of 1-20 carbon atom.
3. the method for claims 1 or 2, wherein the ziegler-natta catalyzed for producing second polyvinyl resin There is at most 15 μm of average particle size (D50), the D50 to be surveyed by the laser diffraction analysis on Malvern type analysis instrument for agent Amount.
4. the method for claims 1 or 2, wherein second polyvinyl resin has monomodal molecular weight distribution.
5. the method for claims 1 or 2, wherein second polyvinyl resin has 0.920-0.960g/cm3Density, it is described Density is measured with ASTM D-1505 standardized tests at a temperature of 23 DEG C.
6. the method for claims 1 or 2, wherein producing the polyvinyl resin in the reactor under slurry conditions.
7. the method for claims 1 or 2, wherein producing the polyvinyl resin in circulation flow reactor.
8. the method for claims 1 or 2, wherein for continuous fusion and setting for first and second polyvinyl resin is being blended Standby middle progress step (c).
9. the method for claim 8, wherein the equipment is extruder and/or mixing machine.
10. the method according to claim 1, wherein the polyethylene product includes the first polyethylene tree of at least 10 weight % Fat, the total weight based on the polyethylene product.
11. the method according to claim 1, wherein the polyethylene product includes the second polyethylene tree of at least 10 weight % Fat, the total weight based on the polyethylene product.
12. method according to claim 5, wherein the polyethylene product has 0.920-0.960g/cm3Density, it is described close Degree is measured with ASTM D-1505 standardized tests at a temperature of 23 DEG C.
CN201280021671.5A 2011-03-04 2012-03-02 Include the preparation method of the polyethylene blend of the resin of resin and the ziegler-nata production of metallocene-produced Active CN103502349B (en)

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